JPH11160838A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material high in maximum density and low in minimum density even in the case of storing it in high temperature and high humidity by using photosensitive silver halide specified value in a silver chloride content or more. SOLUTION: At least one image forming layer formed on the support of the photographic sensitive material contains photosensitive silver halide having a silver chloride content of >=90 mol.% and a dye donor to be allowed to release a diffusible dye by being oxidized, and the dye donor is reductive to silver halide having a latent image in the photosensitive material, and when the silver halide is reduced, the dye donor releases the diffusible dye. It is incorporated in the photosensitive material by dissolving or dispersing it in an organic solvent or an oil substantially immiscible in water, and adding it in a solution or dispersion state to a coating solution, preferably, in an amount of 0.01-10 mmol/m<2> per each layer in order to acquire the sufficient maximum density.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a photosensitive material having a high maximum density and a low minimum density even when a photosensitive material before development or amplification development processing is stored at a high temperature or high humidity. The present invention relates to a silver halide photographic material and an image forming method in which the occurrence of stain when the obtained dye image is stored is reduced.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (hereinafter, also simply referred to as "light-sensitive materials") are extremely superior to other printing materials, such as high sensitivity and excellent gradation. It is widely used today because of its excellent properties. Usually, after the photosensitive material is imagewise exposed, it is immersed in a color developing solution to perform color development.

At present, in the image forming method using the ordinary color developing process which is dominant in the market, the developing process time has been remarkably shortened by practical use of a silver halide emulsion containing silver chloride at a high concentration. However, there are high demands for further reductions in processing time. The so-called mini-lab, which can be installed in a small space and can be easily operated by anyone, has been rapidly increasing by improving equipment such as printers and automatic developing machines, and improving processing solutions and photographic photosensitive materials for photography. There is a demand for a minilab capable of forming images of stable quality with less expensive devices.
In such a minilab, the developer component is generally replenished in accordance with the size of the print and the number of prints, but the number of prints is extremely small, or the processing is performed for a long period of time. In such a case, the replenishment is not sufficiently performed, and the developer is deteriorated by being subjected to air oxidation, and the image quality of the obtained print may be deteriorated.

In order to solve such a problem, a method is known in which a developing agent is previously contained in a light-sensitive material, and processing is performed using an activator solution containing an alkali and, if necessary, a small amount of an auxiliary developing agent. For example, JP-A-57-212441 and JP-A-56-6235 disclose a method of incorporating a paraphenylenediamine-based color developing agent in the form of a salt (so-called precursor) in a photosensitive material. 8-234388, 8-297354
And No. 9-152695 disclose a method of incorporating a sulfonyl hydrazide or carbonyl hydrazide-based color developing agent into a photosensitive material.

In such an image forming method in which a photosensitive material is developed with an activator solution, a decrease in print image quality due to deterioration of the activator solution is reduced. However, a photosensitive material containing a paraphenylenediamine-based developing agent is particularly high in temperature. Alternatively, when stored under high humidity, the white background of the resulting print is liable to deteriorate, and the light-sensitive material containing the sulfonyl hydrazide and carbonyl hydrazide color developing agents in the light-sensitive material is used during storage of the obtained print image. There is a problem that the image density is likely to be reduced and stains are likely to occur, and improvement thereof has been desired.

[0006]

SUMMARY OF THE INVENTION The present invention has a high maximum density and a low minimum density even when a photosensitive material before development or amplification development processing is stored at high temperature or high humidity.
Another object of the present invention is to provide a silver halide photographic light-sensitive material and an image forming method, in which the occurrence of stain when a dye image obtained by development or amplification development is stored is reduced.

[0007]

The above objects of the present invention have been attained by the following constitutions.

(1) A silver halide photograph having at least one layer of a color image forming layer on a support, which contains a photosensitive silver halide and a dye-donating substance which releases a diffusible dye when oxidized. A silver halide photographic light-sensitive material, wherein the silver chloride content of the light-sensitive silver halide is 90 mol% or more.

(2) A silver halide photograph having, on a support, at least one layer of a color image forming layer containing photosensitive silver halide and a dye-donating substance which releases a diffusible dye when oxidized. A silver halide photographic material, characterized in that at least one layer of the photographic material contains an auxiliary developing agent and / or a precursor thereof.

(3) A silver halide photograph having, on a support, at least one layer of a color image forming layer containing a photosensitive silver halide and a dye-donating substance which releases a diffusible dye when oxidized. in the photosensitive material, photosensitive silver halide amount to be contained in the color image forming layer is a silver halide photographic light-sensitive, which is a 0.001g / m ² ~0.1g / m ² in terms of silver material.

(4) A silver halide photograph having at least one layer of a color image forming layer on a support, which contains a photosensitive silver halide and a dye-donating substance which emits a diffusible dye when oxidized. An image forming method for developing a photosensitive material after imagewise exposure, wherein the developing process is an amplification developing process.

(5) The image forming method according to (4), wherein the silver halide photographic material is the silver halide photographic material according to any one of (1) to (3).

(6) The amplification processing is performed by using a first processing liquid containing at least one auxiliary developing agent and a second processing liquid containing at least an oxidizing agent for amplification development. 6. The image forming method according to the above 4 or 5, which is performed.

(7) In an image forming method in which the silver halide photographic light-sensitive material as described in any one of the above items 1 to 3 is imagewise exposed and then developed or amplified and developed, the developing or amplified development is auxiliary development. An image forming method which is carried out in the presence of a main drug and / or a precursor thereof.

(8) An image forming method in which the silver halide photographic light-sensitive material as described in any one of the above items 1 to 3 is imagewise exposed and then developed or amplified and developed. An image forming method, which does not include a step of transferring a sex dye.

(9) In the image forming method, wherein the silver halide photographic light-sensitive material according to any one of the above items 1 to 3, is imagewise exposed and then developed or amplified and developed. An image forming method, which is performed at a temperature of 60 ° C. or lower.

(10) In an image forming method in which the silver halide photographic light-sensitive material according to any one of the above items 1 to 3 is imagewise exposed and then developed or amplified and developed, the silver halide photographic material is released by the developing or amplified development. An image forming method, wherein the dye is removed from the light-sensitive material, and a dye-donating substance remaining in the light-sensitive material is used for image formation.

Hereinafter, the present invention will be described in detail. The light-sensitive material of the present invention is characterized in that it contains a dye-providing substance which releases a diffusible dye when oxidized in the color image forming layer. This dye-donating substance is reducible to silver halide having a latent image in the light-sensitive material, and when the silver halide is reduced (in other words, the dye-donating substance is oxidized), a diffusible dye is released. (A so-called DRR compound).

The DRR compound according to the present invention can be represented by the following general formula (DR).

Formula (DR) (Dye-J) nX In Formula (DR), Dye represents a diffusible dye group, a temporarily shortened diffusible dye group or a dye precursor group; Represents a bond or a divalent linking group, X is reducible to silver halide having a latent image, and undergoes an oxidation-reduction reaction with silver halide directly or via an auxiliary developing agent;
It represents a group that emits Dye by itself being oxidized, and has a property of causing a difference in diffusivity between the released Dye and (Dye-J) nX. n represents 1 or 2, and when n is 2, two (Dye-J) s may be the same or different.

As the dye-donor substance (DRR compound) according to the present invention, known DRR compounds can be used. Representative examples are US Pat. Nos. 3,928,312 and 4,053,312, Nos. 4,055,428, 4,336,322, 3,725,062, 3,728,113, 3,443,939, 4,500,626, JP No. 59-65839, No. 59-69839, No. 48-33826, No. 51-
113624, 59-60434, 59-16
No. 5055, No. 59-124329, No. 53-381
No. 9, No. 51-104343, No. 57-179840
No. 58-16537, and RD (Research Disclosure) 17465.

Specific examples of the dye-providing substance according to the present invention include the compounds described in columns 22 to 44 of the aforementioned US Pat. No. 4,500,626. Compounds (1) to (3), (1)
0) to (13), (16) to (19), (28) to (3)
0), (33) to (35), (38) to (40), (4)
2) to (64) are preferred. Also, U.S. Pat.
Compounds described in column 37 to column 39 of No. 9,408 can also be preferably used.

Hereinafter, specific examples of the dye-providing substance that can be used in the present invention are shown, but the present invention is not limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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The means for incorporating the dye-providing substance according to the present invention into the light-sensitive material is optional. For example, the dye-donating substance may be dissolved in an organic solvent or oil substantially immiscible with water and then dispersed in water or a hydrophilic colloid. A method of adding to a coating solution in a form or a method of adding to a coating solution in the form of a solid fine particle dispersion can be adopted, and these methods can be applied alone or in combination. The amount of the dye-donor added to the light-sensitive material is arbitrary, and depends on the molar extinction coefficient of the released dye and the observation mode of the final image (reflection image or transmission image). In general, it is preferable to use 0.01 to 10 mmol / m ² per color image forming layer. More preferably, the amount is 0.05 to 5 mmol / m ² , and the particularly preferred amount is 0.1 to ² mmol / m ² .

When the oil-in-water emulsion dispersion method is used to add the dye-donating substance or other organic compound according to the present invention, it is usually added to a high-boiling organic solvent, and if necessary, to a low-boiling organic solvent. It is dissolved together with a water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. The high-boiling organic solvent that can be used for dissolving and dispersing the dye-providing substance preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

As a preferred compound as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

In dispersing the dye-providing substance, an anti-fading agent is preferably used in combination to prevent fading of the dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, and Amine compounds represented by the general formula A described in JP-A-64-90445;
General formulas XII, XIII, XIV, XV described in -182741
A metal complex represented by the general formula I 'described in JP-A-1-19649 and
The compound represented by the general formula II described in JP-A-417 is preferred. Also, JP-A-62-215272, 128-1.
37 pages, JP-A-1-161236, pages 17-31,
The discoloration inhibitors described on pages 34 to 39 can also be preferably used.

In the present invention, in order to accelerate the reaction between a dye-donating substance which emits a diffusible dye upon being oxidized and a silver halide having a latent image in a light-sensitive material, the dye-donating substance and a silver halide are used. It is preferable to use a combination of an auxiliary developing agent and / or an auxiliary developing agent precursor that assists electron transfer during the transfer.

Particularly preferably, US Pat. No. 5,139,9
No. 19, European Patent Publication No. 418,743, JP-A-1-1-1
Compounds described in Nos. 38556 and 3-102345 can be used. The auxiliary developing agent preferably has a higher mobility during amplification development than that of the dye-donor substance, and particularly useful auxiliary developing agents are 1-phenyl-3-pyrazolidones or aminophenols.

These auxiliary developing agents and / or their precursors can be added to any layer of the light-sensitive material, but the mode of adding them to the non-photosensitive layer is preferred because the effect of the present invention is high. Means for incorporating these auxiliary developing agents into the light-sensitive material are arbitrary. For example, in addition to the above-described method of adding the dye-providing substance to the light-sensitive material, water or a water-miscible solution such as methanol or ethanol may be used. A method of dissolving in a neutral organic solvent and directly adding to a coating solution, a method of adding to a coating solution as an aqueous solution or a colloidal dispersion in the presence of a surfactant, and the like can be used.These methods can be used alone or in combination. Can be applied. These auxiliary developing agents and / or
Alternatively, the amount of the auxiliary developing agent precursor added to the light-sensitive material is optional, and varies depending on the type and amount of the dye-providing substance contained in the color image-forming layer. Is preferably in the range of 0.01 to 10.
Particularly preferably, it is in the range of 0.05 to 4.

The composition of the silver halide emulsion used in the light-sensitive material according to the present invention is arbitrary, and can be used alone or in combination of a plurality of types of silver halide. When a certain silver chlorobromide, silver chloroiodobromide, silver chloroiodide, silver chloride, or the like is used, the influence of bromide ions and iodide ions acting as catalyst poisons for the amplification development processing is small, so that short amplification development processing is performed. High maximum and low minimum concentrations can be achieved over time, which is a particularly preferred embodiment of the present invention.

As the silver halide emulsion used in the light-sensitive material of the present invention, a silver halide emulsion having a silver chloride content of 90 mol% or more and having a portion containing silver bromide at a high concentration is preferably used. Can be. In this case, the portion containing a high concentration of silver bromide may be a so-called core / shell emulsion in which a complete layer is formed, or a region in which the complete layer is not formed and the composition is merely partially present. In this case, what is called an epitaxy junction may be used.
Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide is present at a high concentration is present at the top of silver halide grains.

The silver halide emulsion used in the light-sensitive material of the present invention may contain a heavy metal ion for the purpose of improving various photographic characteristics. Such heavy metal ions include iron, iridium, platinum, palladium,
Group 8 to 10 metals such as nickel, rhodium, osmium, ruthenium, and cobalt; and cadmium, zinc, and group 12 transition metals such as mercury; lead, rhenium, molybdenum;
Examples include tungsten, gallium, and chromium ions. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These heavy metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand may be cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, or the like.
Examples include chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, and ammonia.
Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to incorporate heavy metal ions into the silver halide emulsion used in the light-sensitive material according to the present invention, the heavy metal ions or a complex containing the heavy metal ions is added before forming silver halide grains and during forming silver halide grains. May be added at any point in each step during physical ripening after the formation of silver halide grains. During the formation of silver halide grains, heavy metal ions or complexes containing them are dissolved together with halide salts. Can be continuously added over the whole or a part of the particle forming process.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly 1 mol
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The shape of the silver halide grains used in the light-sensitive material according to the present invention is arbitrary. One preferred example is
It is a cube having a {100} plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is also preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion used in the light-sensitive material according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at a time, or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant. If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

As silver halide grains used in the light-sensitive material according to the present invention, so-called tabular silver halide is preferably used in order to control gradation balance. As tabular grains containing silver chloride at a high concentration, grains having a {111} major plane and grains having a {100} major plane are known. Particles having a flat surface are particularly preferably used.

The use of tabular silver halide grains in the light-sensitive material of the present invention has the advantage that the bleaching time of the peracid bleaching composition can be shortened, and is particularly preferred.

In the light-sensitive material according to the present invention, an internal latent image type silver halide whose surface is not fogged in advance can be used. For example, US Pat.
206,313, 3,317,322, 3,5
No. 11,622, No. 3,447,927, No. 3,76
Nos. 1,266, 3,703,584, 3,73
No. 6,140 and the like can be used.

The silver halide emulsion used in the light-sensitive material of the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As a chalcogen sensitizer applied to the silver halide emulsion used in the light-sensitive material according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used. Sensitizers are preferred.

In the silver halide emulsion used in the light-sensitive material according to the present invention, fog generated during the step of preparing the light-sensitive material is prevented, performance fluctuation during storage is reduced, and fog generated during development is prevented. Known antifoggants and stabilizers can be used for the purpose. Examples of preferred compounds that can be used for such a purpose are described in
The compound represented by the general formula (II) described in the lower column of page 1 of JP-A-146036 can be exemplified. These compounds are added according to the purpose in a step of preparing a silver halide emulsion, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution and the like.

In the present invention, when an image is formed by amplification and development, the total amount of photosensitive silver halide contained in the photosensitive material is preferably 0.3 g / m ² or less. The amount of silver halide contained therein is preferably 0.1 g / m ² or less. When the amount of silver halide is in the above range, the load on the desilvering treatment is small, and the ratio of the development reaction in the own layer to the influence of the development reaction in the other layer is small, and the stability of gradation reproduction is improved, which is preferable. Preferred silver halide amount of each color image forming layer per are each 0.001 to 0.1 g / m ^2, more preferably in the range of 0.01~0.09g / m ^2.

In the light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or is added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone.

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include those described in JP-A-3-2518.
The dyes of AI-1 to 11 described on page 308 of JP-A-40 and the dyes described in JP-A-6-3770 are preferably used.
General formula (I) described in the lower left column of page 2 of JP-A-750-750,
The compounds represented by (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and do not cause contamination due to residual color.

In order to improve sharpness, the amount of these dyes to be added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferably 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is combined with a yellow dye-donating substance, a magenta dye-donating substance and a cyan dye-donating substance and spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm. And a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye, any of known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 to 8 described in JP-A-3-251840, page 28, alone can be used. Or in combination. As the green photosensitive sensitizing dye, the same publication 2
GS-1 to GS-5 described on page 8 are preferably used.
As the red-sensitive sensitizing dye, R 29 described in
S-1 to S-8 are preferably used. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue light-sensitive sensitizing dyes include supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-6.
Compound S-1 described in No. 6515, pages 15 to 17
It is preferable to use a combination of -S-17.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

In the light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, A hydrophilic colloid such as a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination.
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

As the support used for the light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. which may contain a white pigment can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used.

Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss can be obtained. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoating (adhesion, antistatic properties of the support surface, It may be applied via one or more undercoat layers for improving dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties.

At the time of coating the light-sensitive material according to the present invention, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In the image forming method according to the present invention, for example, as described in JP-A-6-1646,
A method of forming an image by using a diffusible dye transferred to a dye image-receiving material by developing a photosensitive material and a dye image-receiving material while overlapping each other, or by using a dye-donating substance remaining in the photosensitive material after transfer. A method of forming an image, and furthermore, the diffusible dye released by processing with a developer without using a dye image-receiving material is eluted from the light-sensitive material into the processing solution, and a dye-donating substance remaining in the light-sensitive material is removed. Although a method of forming an image by utilizing the method can be used, from the viewpoint of not generating waste material, an image forming method having no dye transfer step is preferable, and furthermore, the amount of silver halide in the photosensitive material is small. From the viewpoint of effective use of resources, a method of forming an image by subjecting a photosensitive material to amplification and development processing is preferable.

Hereinafter, the amplification and development process, which is a preferred image forming method in the present invention, will be described.

In the present invention, the amplification development processing means that a latent image generated by exposure of a photosensitive material is developed with a reducing agent to form developed silver, and an image is formed using a chemical reaction using the developed silver as a catalyst. It is defined as a method of forming or releasing a dye, for example, a method of forming an image dye by a coupling reaction of a coupler with an oxidized color developing agent formed by a redox reaction of a color developing agent and an oxidizing agent using a developed silver catalyst as a catalyst and a developing method. A method of releasing an image dye by a redox reaction between a DRR compound and an oxidizing agent using silver as a catalyst is exemplified.

In the present invention, an alkali solution containing an oxidizing agent for amplification and development can be used as an amplification developer since the dye-donating substance also functions as a reducing agent. To get the lowest concentration,
The above-mentioned embodiment in which the auxiliary developing agent is used in combination is advantageous. This effect is particularly remarkable when the photosensitive material does not contain the auxiliary developing agent. When an oxidizing agent for amplification development and an auxiliary developing agent are used in combination, they may be used in the form of coexisting in the same processing solution, or may be prepared as separate processing solutions. An embodiment in which the oxidizing agent for amplification development is supplied separately is a preferable embodiment because deterioration with time of the processing solution is reduced.

When the auxiliary developing agent and the oxidizing agent for amplification are supplied separately, the oxidizing agent for amplification is 0.001 mol.
/ L to 1 mol / l are preferably used.

When processing is carried out in one bath in which the auxiliary developing agent and the oxidizing agent for amplification are combined, the oxidizing agent for amplification developing is 0.001.
It is preferably used in the range of mol / l to 0.5 mol / l.

When the oxidizing agent for amplification development and the auxiliary developing agent are prepared as separate processing solutions, respectively, these processing solutions are simultaneously or sequentially supplied to the photosensitive material using a spray method or a coating method, And a method of sequentially passing the photosensitive material through a tank filled with the processing liquid.

The oxidizing agent for amplification and development according to the present invention includes:
For example, compounds providing hydrogen peroxide such as hydrogen peroxide, salts of hydrogen peroxide, and adducts of hydrogen peroxide; peroxo compounds such as peroxoborates and peroxocarbonates; and cobalt (III) complexes such as cobalt hexaammine complexes. ,
Halogenous acids such as chlorous acid and periodic acid can be used. Among them, a method using a compound that gives hydrogen peroxide such as hydrogen peroxide, a salt of hydrogen peroxide, and an addition compound of hydrogen peroxide as an oxidizing agent is advantageous because the amplification effect is high and the load on the environment is reduced. It is.

In the image forming method of the present invention, when an auxiliary developing agent is used in the processing solution for amplification and development, its addition amount is optional, but is preferably in the range of about 0.1 g / l to 5 g / l.

Known compounds such as pH buffering agents, inhibitors, preservatives, sequestering agents and surfactants may be added to the photographic processing solution in the amplification developer according to the present invention.

Examples of the pH buffer include potassium or sodium carbonate, sodium or potassium hydrogen carbonate, potassium or sodium borate, potassium or sodium phosphate, disodium or potassium hydrogen phosphate, sodium or potassium dihydrogen phosphate, and water. Calcium oxide, sodium silicate, β-alanine diacetate, arginine, asparagine, ethylenediamine, ethylenediaminetetraacetic acid, ethylenediaminedisuccinate, glycine, histidine, imidazole, isoleucine, leucine, methyliminodiacetic acid, nicotinic acid, nitrilotriacetic acid, piperidine , Proline, purine, and pyrrolidine.

Examples of the inhibitor include halide ions such as chloride ion, bromide ion and iodide ion, or benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, adenine, 1-
Known inhibitors such as phenyl-5 mercaptotetrazole can be mentioned.

Examples of the preservative include known preservatives such as sodium sulfite, potassium sulfite, hydroxylamine and diethylhydroxylamine.

Examples of the sequestering agent include ethylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, iminodiacetic acid, trimethylenetetraaminehexaacetic acid, ethylenediaminetetrapropionic acid, tr
ans-cyclohexane-1,2-diaminetetraacetic acid, ethylenediamine-N, N'-diacetate-N, N'-
Examples thereof include aminopolycarboxylic acids such as dipropionic acid and salts thereof, 1-hydroxy-ethylidene-1,1-diphosphonic acids and salts thereof, catechol disulfonic acids and salts thereof, and pyridine-2-carboxylic acids and salts thereof. In particular, when a sequestering agent having a stability constant with Fe ²⁺ or Ag ⁺ of 5.0 or more is used, the present invention is particularly effective against variations in processing temperature, processing solution supply timing, and the like. This is preferable because the effect of can be stably reproduced.

In the present invention, the processing solution for amplification and development can be used in an arbitrary pH range. However, from the viewpoint of rapid processing and stability of the processing solution, the pH is preferably 9.0 to 12.5, more preferably. It is used in the pH range of 10.5-12.0.

The processing temperature of the amplification development according to the present invention is 20
The temperature is preferably at least 60 ° C and not more than 60 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing liquid and the possibility of fogging, it is preferable that the temperature is not too high, and it is preferable to perform the processing at 25 ° C. or more and 55 ° C. or less.

The amplification development time varies depending on the type of photosensitive material, the processing temperature, the activity of the processing solution, and the like.
It is preferably performed within 0 seconds, more preferably within 90 seconds.

In order to form a photographic image using the photosensitive material according to the present invention, the image recorded on the negative may be optically focused on the photosensitive material to be printed and printed. Also, the image may be once converted into digital information, then the image may be formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed. The printing may be performed by scanning while changing the light intensity or the irradiation time.

The image forming method of the present invention is particularly preferably applied to a photosensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, a photosensitive material for directly forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

In the image forming method of the present invention, after the amplification and development, bleaching and fixing may be performed as necessary. The bleaching process may be performed simultaneously with the fixing process.
After the fixing process, a water washing process is usually performed. Also,
As an alternative to the water washing treatment, a stabilization treatment may be performed.

The processing apparatus used in the image forming method of the present invention may be a roller transport type in which the photosensitive material is transported with rollers interposed in a processing bath, or may be transported with the photosensitive material fixed to a belt. An endless belt method may be used, but a processing bath is formed in a slit shape, and a processing method for supplying a processing liquid to the processing bath and transporting the photosensitive material, and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used.

[0093]

Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.

Example 1 (Preparation of Blue-Sensitive Silver Halide Emulsion (Em-B1)) 4
In 1 liter of a 2% aqueous gelatin solution kept at 0 ° C., the following (solution A1) and (solution B1) were pAg = 7.3, pH =
The solution was added simultaneously while controlling to 3.0, and the following (solution C1) and (solution D1) were simultaneously added while controlling to pAg = 8.0 and pH = 5.5. At this time, the control of pAg is described in
The control of pH was performed using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A1) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B1) 10 g of silver nitrate 200 ml with addition of water 200 ml (Solution C1) 102.7 g of sodium chloride Potassium hexachloroiridium (IV) ate 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Add water 600 ml (Solution D1) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas Demol After desalting using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to obtain an average particle size of 0.57 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1A was obtained. The above-mentioned EMP-1A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to give a blue-sensitive silver halide emulsion (Em-B).
1) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX

[0097]

Embedded image

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole ( Preparation of photosensitive materials (101) to (108)) Basis weight 180
High-density polyethylene was laminated on both sides of g / m ² paper pulp to produce a paper support. However, on the side on which the emulsion layer was applied, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied thereon, to prepare a photosensitive material (101). In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-1) and (H-2) were added as hardening agents. Surfactants (SU-1) as coating aids,
(SU-2) and (SU-3) were added to adjust the surface tension. The total amount of (F-1) was 0.04 g / m ^{2 in} each layer.
Was added so that

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) Third layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 Second layer (blue-sensitive layer) Gelatin 2. 80 Blue-sensitive emulsion (Em-B1) 0.26 Dye donating substance (DR-17) 0.45 DBP 0.18 DIDP 0.18 First layer (gelatin layer) Gelatin 1.00 DIDP 0.002 DBP 002 Support polyethylene-laminated paper The silver halide coating amount was shown in terms of silver.

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium DBP: dibutyl phthalate DIDP: diisodecyl phthalate In the production of the photosensitive material (101), the first layer
A light-sensitive material (1-5-diphenyl-3-pyrazolidone (5PP) was added in the same manner as shown in Table 1 except that the amount of the light-sensitive silver halide in the second layer was changed as shown in Table 1. 102) to (108) were produced.

Preparation of photosensitive materials (109) to (112) After the reflective support used for preparing the photosensitive material (101) was subjected to corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further coated. And a photosensitive material (109) was prepared. In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-1)
(H-2) was added. Surfactants (SU-1), (SU-2) and (SU-3) are added as coating aids,
The surface tension was adjusted. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) Third layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 Second layer (blue-sensitive layer) Gelatin 2. 80 Blue-sensitive emulsion (Em-B1) 0.26 Dye donating substance (M-1) 0.22 Color developing agent (HCD-1) 0.20 DBP 0.10 DIDP 0.10 First layer (gelatin layer) Gelatin 1.00 1,5-diphenyl-3-pyrazolidone 0.02 DIDP 0.002 DBP 0.002 Support Polyethylene laminated paper

[0105]

Embedded image

Incidentally, the coating amount of silver halide was shown by a value converted to silver.

Further, in the preparation of the light-sensitive material (109), except that the amounts of the dye-donor substance, color-developing agent and light-sensitive silver halide in the second layer were changed as shown in Table 1, 110) to (112) were produced.

The photosensitive material (10
Each of 1) to (112) was subjected to
After storing in an environment of 80 ° C. and 80% RH, the solution was placed at 0.degree.
After exposing to light wedge in 5 seconds and performing processing in the following processing step 1,
The reflection density in green light was measured using a densitometer PDA-65 (manufactured by Konica Corporation), and the minimum density (Dmin) and the maximum density (Dmax) were determined.

An image obtained by processing each of the photosensitive materials (101) to (112) in the same manner except that they were stored in an environment of 25 ° C. and 50% RH for 3 days was processed at 80 ° C. and 60% RH.
Was stored for one week in the environment described above, and the degree of increase in the reflection density (yellow stain: ΔDmin) of the lowest density portion in blue light was determined. The results are shown in Table 1.

Processing Step 1 Processing Temperature Temperature Activator Solution (AC-21) 35.0 ± 0.5 ° C. 45 seconds Bleach Solution (BL-1) 30.0 ± 0.5 ° C. 45 seconds Fixer Solution (Fix) -1) 30.0 ± 0.5 ° C for 20 seconds Stabilizing solution 30-34 ° C for 60 seconds Alkaline solution 30-34 ° C for 20 seconds Drying 60-80 ° C for 30 seconds Activator solution (AC-21) Pure water 800 ml Bromide Potassium 0.001 g Potassium chloride 0.35 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-Hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Disodium hydrogen phosphate 10 g Potassium phosphate 20 g Hydrogen peroxide (5.99) %) 25 ml Adjust the pH to 11.5 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Bleaching solution (BL-1) Pure water 800 ml 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g sodium picolinate 4.3 g sodium chloride 11.7 g sodium carbonate 20.0 g potassium dihydrogen phosphate 20 0.0g Hydrogen peroxide (30%) 100ml Adjust the pH to 10.0 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Fixer (Fix-1) Pure water 800 ml Sodium sulfite 100 g Sodium bicarbonate 25 g Water was added to make the total volume 1 liter, and the pH was adjusted to 8.2 with sulfuric acid or potassium hydroxide.

Stabilizing liquid Pure water 800 ml o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1 0.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g Ammonia water (25% aqueous ammonium hydroxide solution) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or ammonia water. I do.

Alkaline solution Pure water 800 ml Potassium carbonate 30 g Water is added to make the total volume 1 liter, and the pH is adjusted to 10.0 with sulfuric acid or potassium hydroxide.

[0115]

[Table 1]

From the results in Table 1, it can be seen that the comparative photosensitive materials (109) incorporating the carbonylhydrazine type color developing agent,
(110) has a relatively low minimum density when stored under high-temperature or high-humidity conditions, has a low maximum density, and has a high yellow stain increase when the obtained image is stored under high-temperature and high-humidity conditions. It turns out that it is not preferable.

The photosensitive materials (111) and (112) containing a p-phenylenediamine-based color developing agent in the form of a tetraphenylboron salt have a relatively small increase in yellow stain in the obtained image. It can be seen that the lowest concentration when stored under high temperature or high humidity conditions is not preferable.

The photosensitive materials (101) to (108) of the present invention
Shows that the minimum density after storage under high-temperature or high-humidity conditions is low, and that the resulting image has a small increase in yellow stain when stored under high-temperature and high-humidity conditions. In particular, photosensitive materials (103) to (108) having an amount of silver halide of 0.1 g / m ² or less have a high maximum density when stored under high-temperature or high-humidity conditions, which is a preferred embodiment of the present invention. Recognize. In addition, photosensitive materials (102), (104), and (1) each having a built-in auxiliary developing agent.
05), (107), and (108) have particularly low minimum concentrations, indicating that they are preferred embodiments of the present invention.

Example 2 (Preparation of silver halide emulsions (Em-B2) and (Em-B3)) (Solution A1) and (Solution C1) used for the preparation of silver halide emulsion EMP-1A of Example 1 To each (A2 solution),
(C2 liquid) except that the average particle diameter was 0.1.
A monodisperse cubic emulsion (EMP-2A) having a grain size of 57 μm and a silver chloride content of 85 mol% was prepared, subjected to the same spectral chemical sensitization as in the preparation of (Em-B1), and subjected to a blue-sensitive silver halide emulsion (Em-B1). B2) was prepared. In addition, (A1 liquid), (C1
Solution) was changed to (A3 solution) and (C3 solution), respectively, to prepare a monodisperse cubic emulsion (EMP-3A) having an average particle size of 0.57 μm and a silver chloride content of 75 mol%,
The same spectral sensitization as in the preparation of (Em-B1) was performed to prepare a blue-sensitive silver halide emulsion (Em-B3).

(Solution A2) Sodium chloride 2.92 g Potassium bromide 1.05 g Water was added to 200 ml (Solution C2) 87.7 g of sodium chloride Potassium hexachloroiridate (IV) 4 × 10 ⁻⁸ mol Hexacyanoiron (II) Potassium acid 2 × 10 ⁻⁵ mol Potassium bromide 31.5 g Water 600 ml (solution A3) Sodium chloride 2.58 g Potassium bromide 1.75 g Water added 200 ml (C3 solution) Sodium chloride 77.4 g Hexachloroiridium (IV) Potassium acid 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 52.4 g Water was added to 600 ml (Preparation of photosensitive materials (201) and (202)) In the preparation of the light-sensitive material (108), the types of the light-sensitive silver halide emulsions were (Em-B2) and (Em-B2). Except for changing as shown in -B3) in the same manner with the photosensitive material (20
1) and (202) were produced.

The photosensitive material (20
1) and (202) were processed and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0122]

[Table 2]

From the results in Table 2, it can be seen that when silver halide having a silver chloride content of 90 mol% or more was used, the minimum density was particularly low, which is a particularly preferred embodiment of the present invention.

Example 3 The photosensitive materials (106) to (108) and (11) of Example 1
In the evaluation of (0) and (112), the evaluation was performed in the same manner except that the processing temperature and the processing time with the activator liquid (AC-21) were changed as shown in Table 3. Table 3 shows the results.

[0125]

[Table 3]

From the results shown in Table 3, it can be seen that when the amplification and development processing using the activator solution was carried out at 60 ° C. or lower, the maximum density was particularly high, which is a preferred embodiment of the present invention.

Example 4 In the evaluation of the photosensitive materials (106) to (108) of Example 1, the amount of 1,5-diphenyl-3-pyrazolidone (5PP) shown in Table 4 was added to the activator solution (AC-21). )
Evaluation was performed in the same manner except that was added. Further, in the evaluation of the photosensitive materials (106) to (108) of Example 1, the evaluation was performed in the same manner except that the amplification and development processing was performed in the following processing step 2 after the imagewise exposure.

Further, the activator solution (AC-21) and the auxiliary developing solution (DS-1) in processing steps 1 and 2 were allowed to stand at 35 ° C. for 5 hours, and the same processing and evaluation were performed.

Processing Step 2 Processing Temperature Temperature Auxiliary developing agent solution (DS-1) 35.0 ± 0.5 ° C. 15 seconds Activator solution (AC-21) 35.0 ± 0.5 ° C. 45 seconds Bleaching solution (BL-1) 30.0 ± 0.5 ° C. 45 seconds Fixing solution (Fix-1) 30.0 ± 0.5 ° C. 20 seconds Stabilizing solution 30-34 ° C. 60 seconds Alkaline solution 30-34 ° C. 20 seconds Dry Drying 60-80 ° C 30 seconds Auxiliary developing agent solution (DS-1) Pure water 800 ml 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Sodium carbonate 20.0 g Potassium dihydrogen phosphate 20.0 g 1.5 -Diphenyl-3-pyrazolidone 1.5 g Adjust the pH to 10.0 with potassium hydroxide or sulfuric acid, and add water to make the total amount 1 liter.

Table 4 shows the results.

[0131]

[Table 4]

From the results in Table 4, it can be seen that the minimum density is particularly low when amplification development processing is performed in the presence of an auxiliary developing agent, which is a particularly preferred embodiment of the present invention. When the amplification processing was performed using the first processing solution containing the auxiliary developing agent and the second processing solution containing the oxidizing agent for amplification development, the processing solution for amplification development stored over time was used. Also in this case, it can be seen that the increase in yellow stain (ΔDmin) when the obtained image is stored under high temperature and high humidity is small, which is a particularly preferred embodiment of the present invention.

Example 5 (Preparation of Green-Sensitive Silver Halide Emulsion (Em-G1)) In the preparation of silver halide emulsion EMP-1A of Example 1, the addition time of (A1 solution) and (B1 solution) and (C1 liquid)
A monodispersed cubic emulsion EMP-11A having an average particle size of 0.30 μm and a silver chloride content of 99.5 mol% was obtained in the same manner as above except that the addition time of the solution (D1) was changed. The above EMP-1
1A was optimally chemically sensitized at 60 ° C. using the following compound to obtain a green light-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion (Em-R1)) Halogenation of Example 1 In the preparation of silver emulsion EMP-1A, the addition time of (A1 solution) and (B1 solution) and (C1 solution)
A monodispersed cubic emulsion EMP-21A having an average particle size of 0.32 μm and a silver chloride content of 99.5 mol% was obtained in the same manner as above except that the addition time of the solution (D1) was changed. EMP-2 above
1A was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R1).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX SS-1 2.0 × 10 ⁻³ mol / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-3 3 × 10 ^-4 mol / mol AgX

[0136]

Embedded image

(Preparation of photosensitive materials (501) to (512)) After the corona discharge treatment was applied to the reflective support prepared in Example 1, a gelatin undercoat layer was provided, and each layer having the following structure was further provided. To prepare a silver halide photographic light-sensitive material (501). In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-
1) and (H-2) were added. Surfactants (SU-1), (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² . The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) Eighth layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 Seventh layer (ultraviolet absorbing layer) Gelatin 0.40 AI-1 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 6th layer (red-sensitive layer) Gelatin 1.30 Red-sensitive emulsion (Em-R1) 0.18 Dye donating substance (DR-18) 0.45 DBP 0.18 DOP 0.18 5th Layer (UV absorbing layer) Gelatin 0.94 UV absorbing agent (UV-1) 0.28 UV absorbing agent (UV-2) 0.09 UV absorbing agent (UV-3) 0.38 AI-1 0.02 Stain Inhibitor (HQ-5) 0. 0 4th layer (green photosensitive layer) Gelatin 1.30 AI-2 0.01 Green photosensitive emulsion (Em-G1) 0.14 Dye donating substance (DR-17) 0.20 DIDP 0.13 DBP 13 Third layer (intermediate layer) Gelatin 1.20 AI-3 0.01 Stain inhibitor (HQ-1) 0.03 Stain inhibitor (HQ-3) 0.03 Stain inhibitor (HQ-4) 05 Stain inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Optical brightener (W-1) 0.10 Second layer (blue-sensitive layer) Gelatin 1.20 Blue-sensitive emulsion ( Em-B1) 0.26 Dye donating substance (DR-7) 0.50 DBP 0.25 DNP 0.20 First layer (gelatin layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Support Polyethylene laminated paper In addition, c Gen silver coating amount is expressed by the value in terms of silver.

DOP: dioctyl phthalate DNP: dinonyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2 5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone In the preparation of the photosensitive material (501), 1,5-diphenyl-3-pyrazolidone (5
PP) was added as shown in Table 5, and the amount of photosensitive silver halide in the second, fourth and sixth layers was changed as shown in Table 5. ~ (50
8) was produced.

Preparation of photosensitive materials (509) to (512) After the reflective support used for preparing the photosensitive material (501) was subjected to corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following structure was further coated. And a photosensitive material (509) was prepared. In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-1)
(H-2) was added. Surfactants (SU-1), (SU-2) and (SU-3) are added as coating aids,
The surface tension was adjusted. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² . The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) Eighth layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 Seventh layer (ultraviolet absorbing layer) Gelatin 0.40 AI-1 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 6th layer (red-sensitive layer) Gelatin 1.30 Red-sensitive emulsion (Em-R1) 0.18 Dye donating substance (C-1) 0.40 Color developing agent (HCD-1) 0. 40 DBP 0.18 DOP 0.18 Fifth layer (ultraviolet absorbing layer) Gelatin 0.94 1,5-diphenyl-3-pyrazolidone 0.10 Ultraviolet absorbing agent (UV-1) 0.28 Ultraviolet absorbing agent (UV- 2) 0.09 UV Absorbent (UV-3) 0.38 AI-1 0.02 Stain inhibitor (HQ-5) 0.10 Fourth layer (green-sensitive layer) Gelatin 1.30 AI-2 0.01 Green-sensitive emulsion (Em-G1) 0.14 Dye donating substance (M-1) 0.22 Color developing agent (HCD-1) 0.20 DIDP 0.13 DBP 0.13 Third layer (intermediate layer) Gelatin 1.20 AI -3 0.01 Stain inhibitor (HQ-1) 0.03 Stain inhibitor (HQ-3) 0.03 Stain inhibitor (HQ-4) 0.05 Stain inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Optical brightener (W-1) 0.10 Second layer (blue-sensitive layer) Gelatin 1.20 Blue-sensitive emulsion (Em-B1) 0.26 Dye-donating substance (Y- 1) 0.40 Color developing agent (HCD-1) 0.40 BP 0.20 DNP 0.20 First layer (gelatin layer) Gelatin 1.00 1,5-diphenyl-3-pyrazolidone 0.05 DIDP 0.002 DBP 0.002 Support polyethylene laminated paper In addition, silver halide coated The amounts are shown in terms of silver.

In the preparation of the light-sensitive material (509), the amounts of the dye-donating substances, color-developing agents and photosensitive silver halide in the second, fourth and sixth layers were changed as shown in Table 5. In the same manner, the photosensitive materials (510) to (51)
2) was produced.

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

The photosensitive material (50
The same processes and evaluations as in Example 1 were performed on 1) to (512). The results are shown in Table 5.

[0147]

[Table 5]

From the results shown in Table 5, comparative photosensitive materials (509) incorporating a carbonylhydrazine type color developing agent,
(510) has a relatively low minimum density when stored under high-temperature or high-humidity conditions, but has a low maximum density. Further, the obtained image has a yellow stain (ΔDmin) when stored under high-temperature and high-humidity conditions. It can be seen that the rise is high, which is not preferable. The photosensitive materials (511) and (512) containing a p-phenylenediamine-based color developing agent in the form of tetraphenylboron salt have a relatively small increase in yellow stain (ΔDmin) of the obtained image. It can be seen that the lowest concentration when stored under high temperature or high humidity conditions is not preferable.

The photosensitive materials (501) to (508) of the present invention
Shows that the minimum density after storage under high-temperature or high-humidity conditions is low, and the increase in yellow stain (ΔDmin) when the obtained image is stored under high-temperature and high-humidity conditions is small. Especially when the silver halide content is 0.1
g / m ² or less photosensitive materials (503) to (508)
Is high in the maximum concentration when stored under high-temperature or high-humidity conditions, indicating that this is a preferred embodiment of the present invention. In addition, a photosensitive material (50
2), (504), (505), (507), (50)
8) shows that the minimum concentration is particularly low and is a preferred embodiment of the present invention.

[0150]

According to the present invention, even when the photosensitive material before development or amplification development processing is stored at high temperature or high humidity, it has a high maximum density and a low minimum density and can be obtained by development or amplification development. Thus, a silver halide photographic light-sensitive material and an image forming method in which the generation of stain when the dye image is preserved is reduced can be provided.

Claims (10)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one layer of a color image forming layer on a support, which comprises a photosensitive silver halide and a dye-donating substance which releases a diffusible dye when oxidized. A silver halide photographic material, wherein the silver halide content of the photosensitive silver halide is 90 mol% or more. 2. A silver halide photographic light-sensitive material comprising at least one layer of a color image-forming layer on a support, which comprises a photosensitive silver halide and a dye-donating substance which emits a diffusible dye when oxidized. A silver halide photographic light-sensitive material, characterized in that at least one layer of the material contains an auxiliary developing agent and / or a precursor thereof. 3. A silver halide photographic light-sensitive material having at least one layer of a color image-forming layer on a support, which comprises a photosensitive silver halide and a dye-donating substance which releases a diffusible dye when oxidized. In the material, the amount of the photosensitive silver halide contained in the color image forming layer is 0.00.0
A silver halide photographic light-sensitive material characterized in that the photographic material has an amount of from 0.1 g / m ^{2 to} 0.1 g / m ² . 4. A silver halide photographic light-sensitive material comprising at least one layer of a color image-forming layer on a support, which comprises a photosensitive silver halide and a dye-donating substance which releases a diffusible dye when oxidized. An image forming method for developing a material after imagewise exposing the material, wherein the developing process is an amplification developing process. 5. The image forming method according to claim 4, wherein said silver halide photographic light-sensitive material is the silver halide photographic light-sensitive material according to claim 1. 6. The amplification processing is carried out using a first processing liquid containing at least one auxiliary developing agent and a second processing liquid containing at least an oxidizing agent for amplification development. The image forming method according to claim 4, wherein the image is formed. 7. An image forming method for developing or amplifying and developing the silver halide photographic light-sensitive material according to claim 1 after imagewise exposure, wherein the developing or the amplifying development is an auxiliary development. An image forming method which is carried out in the presence of a main drug and / or a precursor thereof. 8. An image forming method for developing or amplifying and developing the silver halide photographic light-sensitive material according to claim 1 after imagewise exposure, wherein the diffusion emitted by the developing or the amplifying development is carried out. An image forming method, which does not include a step of transferring a sex dye. 9. An image forming method for developing or amplifying and developing the silver halide photographic material according to claim 1 after imagewise exposure, wherein the developing or amplifying development is performed at 20 ° C. An image forming method, which is performed at a temperature of 60 ° C. or lower. 10. An image forming method for developing or amplifying and developing the silver halide photographic light-sensitive material according to claim 1 after imagewise exposure, wherein the silver halide photographic material is released by the developing or amplifying development. An image forming method, wherein the dye is removed from the light-sensitive material, and a dye-donating substance remaining in the light-sensitive material is used for image formation.